EP1441402B1 - Alkalin-trockenzelle - Google Patents

Alkalin-trockenzelle Download PDF

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Publication number
EP1441402B1
EP1441402B1 EP02775367A EP02775367A EP1441402B1 EP 1441402 B1 EP1441402 B1 EP 1441402B1 EP 02775367 A EP02775367 A EP 02775367A EP 02775367 A EP02775367 A EP 02775367A EP 1441402 B1 EP1441402 B1 EP 1441402B1
Authority
EP
European Patent Office
Prior art keywords
positive electrode
weight
alkaline dry
parts
tio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02775367A
Other languages
English (en)
French (fr)
Other versions
EP1441402A4 (de
EP1441402A1 (de
Inventor
Mitsuji Adachi
Takayuki Umebayashi
Yasuhiko Shoji
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Corp
Original Assignee
Panasonic Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Panasonic Corp filed Critical Panasonic Corp
Publication of EP1441402A1 publication Critical patent/EP1441402A1/de
Publication of EP1441402A4 publication Critical patent/EP1441402A4/de
Application granted granted Critical
Publication of EP1441402B1 publication Critical patent/EP1441402B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H01M6/08—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with cup-shaped electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/06—Electrodes for primary cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0014—Alkaline electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an alkaline dry battery which has an excellent positive electrode utilization rate during discharge under a heavy load and an intermediate load, and in which a decrease in electrical capacity during discharge under a light load is suppressed.
  • the conventional alkaline dry batteries have employed, as a positive electrode additive, an anatase titanium oxide (e.g., Japanese Laid-Open Patent Publication No. Hei 8-510355 ), a titanium-containing composite oxide (e.g., Japanese Laid-Open Patent Publication No. Hei 9-139201 ) and a barium compound such as barium sulfate (e.g., International Publication No. WO 00/30198 ).
  • an anatase titanium oxide e.g., Japanese Laid-Open Patent Publication No. Hei 8-510355
  • a titanium-containing composite oxide e.g., Japanese Laid-Open Patent Publication No. Hei 9-139201
  • barium compound such as barium sulfate
  • titanium oxide a titanium-containing composite oxide or a barium compound
  • a positive electrode improves the heavy load discharge characteristic to some extent, it does not yield a sufficient active material utilization rate.
  • conventional additives in order for the aforesaid conventional additives to provide sufficient effects, they need to be employed in a large amount. Accordingly, a filled amount of manganese dioxide which serves as an active material in the positive electrode decreases, thereby decreasing the electrical capacity of the battery and reducing the light load discharge characteristic thereof. This also causes a great inconvenience for the use of equipment such as timepieces which require discharging under a light load, since there still exists a considerable demand for alkaline dry batteries.
  • the present invention provides an alkaline dry battery which comprises: a negative electrode; an alkaline electrolyte; and a positive electrode comprising manganese dioxide and a graphite powder, characterized in that the positive electrode comprises an additive selected from the group consisting of Ti(OH) 4 and TiO(OH) 2 , and wherein the positive electrode comprises 0.01 to 5 parts by weight of the additive per 100 parts by weight of manganese dioxide.
  • the average particle size of TiO(OH) 2 is preferably 10 -9 to 10 -8 m.
  • the present invention improves the positive electrode active material utilization rate during discharge under a heavy load and an intermediate load by containing at least one selected from the group consisting of Ti(OH) 4 and TiO(OH) 2 in the positive electrode.
  • the proportion of the positive electrode active material in the positive electrode material mixture is reduced by the addition of the aforesaid additives to the positive electrode, the filling properties of the positive electrode material mixture are improved by the addition and the filled amount of the positive electrode active material increases under the same molding conditions since these additives have functions as a binder.
  • the addition of the aforesaid additives in the amount range in accordance with the present invention therefore does not decrease the filled amount of the positive electrode active material, so that reduction in light load discharge characteristic can be suppressed.
  • the feature of the present invention lies in that the positive electrode comprises manganese dioxide as a positive electrode active material, a graphite powder as a conductive agent and at least one selected from the group consisting of Ti(OH) 4 and TiO(OH) 2 as an additive.
  • TiO(OH) 2 in the present invention is in the form of fine powder and has a particle size of 10 -9 to 10 -8 m, which is much smaller than particle sizes (10 -7 to 10 -5 m) of anatase titanium oxides conventionally used as positive electrode additives and, therefore, TiO(OH) 2 has a larger contact area with the positive electrode active material when added to the positive electrode in a certain amount. Accordingly, an effect greater than conventional effects can be obtained by the addition of a small amount of TiO(OH) 2 , and this is desirable as the additive.
  • a particle size of greater than 10 -8 m results in a decreased surface area of the particles, reducing the effect thereof.
  • these additives when added to a material mixture comprising manganese dioxide and a graphite powder, these additives also function as a binder to improve the moldability of the positive electrode, thereby providing the effect of increasing the filled amount thereof.
  • the positive electrode comprises 0.01 to 5 parts by weight of at least one selected from the group consisting of Ti(OH) 4 and TiO(OH) 2 per 100 parts by weight of manganese dioxide.
  • the reason is that the content of less than 0.01 part by weight results in insufficient improvement in heavy load and light load discharge characteristics, and the content of more than 5 parts by weight causes reduction in light load discharge characteristic. Further, containing 0.5 to 3 parts by weight per 100 parts by weight of manganese dioxide is particularly preferred.
  • manganese dioxide and the graphite powder conventionally used ones may be used.
  • negative electrode and the alkaline electrolyte conventionally used ones can be employed.
  • FIG. 1 shows a front view, partly in cross section, of an alkaline dry battery fabricated in examples of the present invention.
  • a battery case 1 accommodates therein a positive electrode material mixture 2 molded into short cylindrical pellets, a gel negative electrode 3 and a separator 4.
  • a steel case whose inner surface is nickel-plated can be employed.
  • a plurality of positive electrode material mixtures 2 are placed in intimate contact with the inner surface of the battery case 1.
  • the separator 4 is disposed inside the positive electrode material mixture 2, and the inside thereof is filled with the gel negative electrode 3.
  • the positive electrode material mixture 2 was prepared as follows:
  • manganese dioxide and graphite were mixed in a weight ratio of 90:10, and Ti(OH) 4 was further added in predetermined amounts (x part(s) by weight) listed in Table 1 per 100 parts by weight of manganese dioxide, followed by mixing. It is to be noted that Ti(OH) 4 used in the present example had an average particle size of 10 -6 m. Three parts by weight of an alkaline electrolyte was added per 100 parts by weight of the obtained mixture, which was sufficiently stirred and then compression molded into flakes.
  • the positive electrode material mixture in flake form was pulverized into granules, followed by classifying with a sieve, and those having 10 to 100 mesh were compression molded into hollow cylindrical shape to give the positive electrode material mixture 2 in pellet form.
  • Two pieces of this positive electrode material mixture 2 were inserted into the battery case 1, and then remolded by means of a compressing jig so as to be placed intimate contact with the inner wall of the battery case 1.
  • a separator 4 having a bottom and cylindrical shape was disposed at the center of the positive electrode material mixture 2 placed inside the battery case 1, and a predetermined amount of an alkaline electrolyte was injected into the separator 4. After an elapse of a predetermined time, the separator 4 was filled with the gel negative electrode 3 comprising an alkaline electrolyte, a gelling agent and a zinc powder.
  • the gel negative electrode 3 a gel comprising 1 part by weight of sodium polyacrylate as a gelling agent, 33 parts by weight of 40 wt% sodium hydroxide as an alkaline electrolyte and 66 parts by weight of the zinc powder was employed.
  • non-woven fabric made mainly of polyvinylalcohol fibers and rayon fibers was used.
  • a negative electrode current collector 6 was inserted in the center of the gel negative electrode 3. It should be noted that a gasket 5 and a bottom plate 7 serving as a negative electrode terminal were combined integrally with the negative electrode current collector 6.
  • the opening end of the battery case 1 was clamped to the periphery of the bottom plate 7, with the end of the gasket 5 disposed therebetween, to seal the opening of the battery case 1.
  • the outermost surface of the battery case 1 was covered with an outer jacket label 8, thereby giving an alkaline dry battery.
  • the alkaline dry batteries thus obtained were evaluated in the following manner.
  • the alkaline dry battery in fresh state (immediately after fabrication) was continuously discharged with a 2.2 ⁇ load until the off-load voltage reached 0.9 V to measure the discharge duration time.
  • the heavy load discharge characteristic was represented as an index. The results of the evaluation were shown in Table 1.
  • the intermediate load discharge characteristic was evaluated in the same manner as in the case of the heavy load discharge characteristic, except that the battery was continuously discharged with a 10 ⁇ load.
  • the light load discharge characteristic was evaluated in the same manner as in the case of the heavy load discharge characteristic, except that the battery was continuously discharged with a 39 ⁇ load. The results of these evaluations were also shown in Table 1.
  • Positive electrode material mixtures 2 were prepared in the same manner as in Example 1, except for adding TiO(OH) 2 , in place of the positive electrode additive Ti(OH) 4 , in predetermined amounts (x part(s) by weight) listed in Table 1 per 100 parts by weight of manganese dioxide, to obtain alkaline dry batteries.
  • the characteristics of the alkaline dry batteries were evaluated in the same manner as in Example 1. It is to be noted that TiO(OH) 2 used in the present example had an average particle size of 10 -9 m.
  • Positive electrode material mixtures 2 were produced in the same manner as in Example 1, except for adding TiO 2 , in place of the positive electrode additive Ti(OH) 4 , in predetermined amounts (x part(s) by weight) listed in Table 1 per 100 parts by weight of manganese dioxide to obtain alkaline dry batteries. It is to be noted that TiO 2 had an average particle size of 10 -6 m. The characteristics of the alkaline dry batteries were evaluated in the same manner as in Example 1. Table 1 Example No. Amount added (part(s) by weight) Discharge duration time Discharge duration time TiO 2 Ti(OH) 4 TiO(OH) 2 2.2 ⁇ 10 ⁇ 39 ⁇ Com. Ex.1 0 0 0 100 100 100 Com. Ex.2 0.1 0 0 100 101 100 Com.
  • Example 5 With respect to the added amount of 1 part by weight, which is considered as optimum, the improvement in characteristics was greater in Example 5 than in Example 2. The reason was presumably that TiO(OH) 2 had a particle size of 10 -9 m, which was smaller than that of Ti(OH) 4 and thus yielded a larger contact area with the positive electrode active material when added in the same amount, thereby achieving a greater effect of improving the characteristics.
  • an alkaline dry battery which has excellent heavy load and intermediate load discharge characteristics, and in which reduction in light load discharge characteristic is suppressed.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Primary Cells (AREA)

Claims (3)

  1. Alkalische Trockenbatterie, die umfasst:
    eine negative Elektrode; einen alkalischen Elektrolyten; und eine positive Elektrode, die Mangandioxid und ein Graphitpulver umfasst, dadurch gekennzeichnet, dass die positive Elektrode ein aus der aus Ti(OH)4 und TiO(OH)2 bestehenden Gruppe ausgewähltes Additiv umfasst; und
    wobei die positive Elektrode 0,01 bis 5 Gewichtsteile des Additivs pro 100 Gewichtsteile Mangandioxid umfasst.
  2. Alkalische Trockenbatterie nach Anspruch 1, wobei die positive Elektrode 0,5 bis 3 Gewichtsteile des Additivs pro 100 Gewichtsteile Mangandioxid umfasst.
  3. Alkalische Trockenbatterie nach einem der Ansprüche 1 bis 2, wobei die positive Elektrode TiO(OH)2 mit einer durchschnittlichen Teilchengröße von 10-9 bis 10-8 m als das Additiv umfasst.
EP02775367A 2001-11-01 2002-10-17 Alkalin-trockenzelle Expired - Lifetime EP1441402B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2001336580 2001-11-01
JP2001336580 2001-11-01
PCT/JP2002/010807 WO2003038932A1 (en) 2001-11-01 2002-10-17 Alkaline dry cell

Publications (3)

Publication Number Publication Date
EP1441402A1 EP1441402A1 (de) 2004-07-28
EP1441402A4 EP1441402A4 (de) 2007-06-20
EP1441402B1 true EP1441402B1 (de) 2010-04-21

Family

ID=19151381

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02775367A Expired - Lifetime EP1441402B1 (de) 2001-11-01 2002-10-17 Alkalin-trockenzelle

Country Status (11)

Country Link
US (1) US7405023B2 (de)
EP (1) EP1441402B1 (de)
KR (1) KR20050037489A (de)
CN (1) CN1248343C (de)
AT (1) ATE465522T1 (de)
AU (1) AU2002343998C1 (de)
BR (1) BR0212955B1 (de)
CA (1) CA2463849A1 (de)
DE (1) DE60236100D1 (de)
HK (1) HK1063882A1 (de)
WO (1) WO2003038932A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104160529B (zh) 2012-12-20 2017-06-23 松下知识产权经营株式会社 碱性电池
CN110739459A (zh) * 2019-10-12 2020-01-31 宁波倍特瑞能源科技有限公司 一种半固态电池正极材料及其制备的碱性锌锰电池

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3689219A (en) * 1971-05-24 1972-09-05 Vanderbilt Co R T Process of precipitating h2tio3
DE3327568A1 (de) 1983-07-30 1985-02-07 Ernst 7326 Heiningen Weichel Mehrfach-geraetekombination fuer traktoren zur bodenlockerung, saatbettherrichtung und bestellung
DE3337568A1 (de) * 1983-10-15 1985-04-25 Varta Batterie Ag, 3000 Hannover Herstellung von elektrolytischem braunstein fuer alkalische zellen
US5342712A (en) * 1993-05-17 1994-08-30 Duracell Inc. Additives for primary electrochemical cells having manganese dioxide cathodes
US5599644A (en) * 1995-06-07 1997-02-04 Eveready Battery Company, Inc. Cathodes for electrochemical cells having additives
US5569564A (en) 1995-06-07 1996-10-29 Eveready Battery Company, Inc. Alkaline cell having a cathode including a titanate additive
US5744266A (en) * 1996-02-02 1998-04-28 Matsushita Electric Industrial Co., Ltd. Batteries and a method of manufacturing positive active material for the batteries
JPH10308217A (ja) * 1997-03-06 1998-11-17 Matsushita Electric Ind Co Ltd アルカリ乾電池
US5865646A (en) 1997-03-07 1999-02-02 Berg Technology, Inc. Connector shield with integral latching and ground structure
GB9713683D0 (en) * 1997-06-27 1997-09-03 Battery Technologies Inc Additives for rechargeable alkaline manganese dioxide cells
JP2002530815A (ja) * 1998-11-13 2002-09-17 エヴァレディー バッテリー カンパニー インコーポレイテッド 電極添加剤を含む電気化学的電池
JP3897743B2 (ja) 2002-07-30 2007-03-28 日東電工株式会社 光学フィルムの製造方法
JP4056322B2 (ja) * 2002-08-09 2008-03-05 松下電器産業株式会社 アルカリ乾電池
US7294429B2 (en) * 2003-01-03 2007-11-13 The Gillette Company Alkaline cell with flat housing

Also Published As

Publication number Publication date
BR0212955A (pt) 2004-10-13
CN1565064A (zh) 2005-01-12
ATE465522T1 (de) 2010-05-15
DE60236100D1 (de) 2010-06-02
CA2463849A1 (en) 2003-05-08
CN1248343C (zh) 2006-03-29
EP1441402A4 (de) 2007-06-20
BR0212955B1 (pt) 2011-07-26
WO2003038932A1 (en) 2003-05-08
US7405023B2 (en) 2008-07-29
KR20050037489A (ko) 2005-04-22
US20040258994A1 (en) 2004-12-23
AU2002343998B2 (en) 2008-01-24
AU2002343998C1 (en) 2008-07-24
HK1063882A1 (en) 2005-01-14
EP1441402A1 (de) 2004-07-28

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